The present invention relates to a fabric softener composition and to a process for the bleaching of textile fibre materials using this fabric softener composition.
In customary household washing processes for whites, such as bed linen, table linen and white cotton fabrics, the laundry items to be treated are normally subjected to a combined washing and bleaching process in which the items of laundry are treated in an aqueous bath comprising, as active substance, an organic detergent and a bleach. Processes for bleaching or removing stains from textiles using water-soluble phthalocyanine compounds are known, for example, from U.S. Pat. Nos. 3,927,967, 4,094,806 and 4,033,718.
The object of the present invention is to use water-soluble phthalocyanine compounds as photobleaching agents in certain fabric softener compositions comprising, as active substance, ester quats, which are quaternary ammonium compounds having at least one long-chain hydrophobic alkyl or alkenyl group interrupted by carboxyl groups. Fabric softeners containing ester quats are described, for example, in EP-A-0 239 910 or WO 95/24460.
Surprisingly, it has now been found that fabric softener compositions comprising water-soluble phthalocyanine compounds of a cationic, neutral or anionic nature bring about particularly good bleaching effects if textiles are treated in an aqueous fabric softener bath comprising these compositions, the textiles being irradiated with light in the visible and/or infrared region or in the daylight in the fabric softener bath itself or subsequently in the damp state.
The present invention thus relates to a fabric softener composition comprising
(a) a water-soluble phthalocyanine of Zn, Fe(II), Ca, Mg, Na, K, Al, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV), In(III), Sn(IV) or Hf(VI); and
(b) a quaternary ammonium compound of the formula 
xe2x80x83in which
R1 and R2 independently of one another are C1-C5alkyl; or hydroxy-C1-C5alkyl;
A is the radical of the formula 
or the radical of the formula 
B is C1-C5alkyl; a C8-C20 fatty acid radical; the radical of the formula (1a) or the, radical of the formula (1b);
R3, R4 and R5 independently of one another are a C8-C20 fatty acid radical;
X1xe2x88x92 is a softener-compatible anion; and
m, n and p are numbers from 0 to 5.
The novel composition advantageously comprises, as photobleaching agent, a compound of the formula 
in which
PC is the phthalocyanine ring system;
Me is Zn, Fe(II), Ca, Mg, Na, K, Alxe2x80x94Z1, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV), In(III), Sn(IV) or Hf(VI);
Z1 is a halide, sulfate, nitrate, carboxylate, alkanolate, or hydroxyl ion;
q is 0, 1 or 2;
r is 1 to 4;
Q1 is a sulfo or carboxyl group; or a radical of the formula
xe2x80x94SO2X2xe2x80x94R6xe2x80x94X3+, xe2x80x94Oxe2x80x94R6xe2x80x94X3+; or xe2x80x94(CH2)txe2x80x94Y1+;
xe2x80x83in which
R6 is a branched or unbranched C1-C8alkylene; or 1,3- or 1,4-phenylene;
X2 is xe2x80x94NHxe2x80x94; or xe2x80x94Nxe2x80x94C1-C5alkyl;
X3+ is a group of the formula 
xe2x80x83or, in the case where R6=C1-C8alkylene, also a group of the formula 
Y1+ is a group of the formula 
t is 0 or 1;
where in the above formulae
R7 and R8 independently of one another are C1-C6alkyl;
R9 is C1-C6alkyl; C5-C7cycloalkyl; or NR11R12;
R10 and R11 independently of one another are C1-C5alkyl;
R12 and R13 independently of one another are hydrogen or C1-C5alkyl;
R14 and R15 independently of one another are unsubstituted C1-C6alkyl or C1-C6alkyl substituted by hydroxyl, cyano, carboxyl, carb-C1-C6alkoxy, C1-C6alkoxy, phenyl, naphthyl or pyridyl;
u is from 1 to 6;
A1 is a unit which completes an aromatic 5- to 7-membered nitrogen heterocycle, which may where appropriate also contain one or two further nitrogen atoms as ring members, and
B1 is a unit which completes a saturated 5- to 7-membered nitrogen heterocycle, which may where appropriate also contain 1 to 2 nitrogen, oxygen and/or sulfur atoms as ring members;
Q2 is hydroxyl; C1-C22alkyl; branched C4-C22alkyl; C2-C22alkenyl; branched C4-C22alkenyl and mixtures thereof; C1-C22alkoxy; a sulfo or carboxyl radical; a radical of the formula 
xe2x80x83a branched alkoxy radical of the formula 
xe2x80x83an alkylethyleneoxy unit of the formula xe2x80x94(T1)dxe2x80x94(CH2)b(OCH2CH2)axe2x80x94B3 or an ester of the formula COOR23 in which
B2 is hydrogen; hydroxyl; C1-C30alkyl; C1-C30alkoxy; xe2x80x94CO2H; xe2x80x94CH2COOH; SO3xe2x88x92M1+; xe2x80x94OSO3xe2x88x92M1+; xe2x80x94PO32xe2x88x92M1; xe2x80x94OPO32xe2x88x92M1; and mixtures thereof;
B3 is hydrogen; hydroxyl; xe2x80x94COOH; xe2x80x94SO3xe2x88x92M1+; xe2x80x94OSO3xe2x88x92M1+; C1-C6alkoxy;
M1 is a water-soluble cation;
T1 is xe2x80x94Oxe2x80x94; or xe2x80x94NHxe2x80x94;
X1 and X4 independently of one another are xe2x80x94Oxe2x80x94; xe2x80x94NHxe2x80x94; or xe2x80x94Nxe2x80x94C1-C5alkyl;
R16 and R17 independently of one another are hydrogen, a sulfo group and salts thereof, a carboxyl group and salts thereof or a hydroxyl group, at least one of the radicals R16 and R17 being a sulfo or carboxyl group or salts thereof,
Y2 is xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94NHxe2x80x94or xe2x80x94Nxe2x80x94C1-C5alkyl;
R18 and R19 independently of one another are hydrogen, C1-C6alkyl, hydroxy-C1-C6alkyl, cyano-C1-C6alkyl, sulfo-C1-C6alkyl, carboxy or halogen-C1-C6alkyl; unsubstituted phenyl or phenyl substituted by halogen, C1-C4alkyl or C1-C4alkoxy, sulfo or carboxyl or R18 and R19 together with the nitrogen atom to which they are bonded are a saturated 5- or 6-membered heterocyclic ring which may additionally also contain a nitrogen or oxygen atom as a ring member;
R20 and R21 independently of one another are C1-C6alkyl or aryl-C1-C6alkyl radicals;
R22 is hydrogen; an unsubstituted C1-C6alkyl or C1-C6alkyl substituted by halogen, hydroxyl, cyano, phenyl, carboxyl, carb-C1-C6alkoxy or C1-C6alkoxy;
R23 is C1-C22alkyl, branched C4-C22alkyl, C1-C22alkenyl or branched C4-C22alkenyl; C3-C22glycol; C1-C22alkoxy; branched C4-C22alkoxy; and mixtures thereof;
M is hydrogen; or an alkali metal ion or ammonium ion,
Z2 is a chlorine, bromine, alkylsulfate or aralkylsulfate ion;
a is 0 or 1;
b is from 0 to 6;
c is from 0 to 100;
d is 0; or 1;
e is from 0 to 22;
v is an integer from 2 to 12;
w is 0 or 1; and
A is an organic or inorganic anion, and
s is equal to r in cases of monovalent anions Axe2x88x92 and is xe2x89xa6r in cases of polyvalent anions, it being necessary for Asxe2x88x92 to compensate the positive charge; where, when rxe2x89xa01, the radicals Q1 can be identical or different,
and where the phthalocyanine ring system may also comprise further solublising groups.
The number of substituents Q1 and Q2 in the formula (2a) and (2b) respectively, which may be identical or different, is between 1 and 8, and it is not imperative, as is generally the case with phthalocyanines, for it to be an integer (degree of substitution). If other noncationic substituents are present, the sum of the latter and the cationic substituents is between 1 and 4. The minimum number of substituents which must be present in the molecule is governed by the solubility of the resulting molecule in water. It is sufficiently soluble in water when enough of the phthalocyanine compound dissolves to effect a photodynamically catalysed oxidation on the fibre. A solubility as low as 0.01 mg/l may suffice, although one of from 0.001 to 1 g/l is generally advantageous.
Halogen means fluorine, bromine or, in particular, chlorine.
Especially suitable groups 
are: 
Preference is given to the group 
Suitable heterocyclic rings in the group 
are likewise the groups listed above, the bond to the other substituents merely being via a carbon atom.
In all of these substituents, phenyl, naphthyl and aromatic hetero rings may be substituted by one or two further radicals, for example by C1-C6alkyl, C1-C6alkoxy, halogen, carboxyl, carb-C1-C6alkoxy, hydroxyl, amino, cyano, sulfo, sulfonamido, etc.
Preference is given to a substituent from the group C1-C6alkyl, C1-C6alkoxy, halogen, carboxyl, carb-C1-C6alkoxy or hydroxyl.
Particularly suitable groups 
are: 
All of the aforementioned nitrogen heterocycles can also be substituted by alkyl groups, either on a carbon atom or on another nitrogen atom in the ring. The alkyl group is preferably the methyl group.
Axe2x88x92s in formula (2a) is, as a counterion to the positive charge on the remainder of the molecule, any anion. In general, it is introduced by the preparation process (quaternization). It is then preferably a halogen ion, an alkylsulfate or an arylsulfate ion. Arylsulfate ions which may be mentioned are the phenylsulfonate, p-tolylsulfonate and the p-chlorophenylsulfonate ion. The anion can however also be any other anion since the anions can be readily exchanged in a known manner; Asxe2x88x92 can thus also be a sulfate, sulfite, carbonate, phosphate, nitrate, acetate, oxalate, citrate, lactate ion or another anion of an organic carboxylic add. The index s is the same as r for monovalent anions. For polyvalent anions, s has a value xe2x89xa6r, in which case it must be chosen, depending on the conditions, such that it exactly balances the positive charge on the remainder of the molecule.
C1-C6alkyl and C1-C6alkoxy are straight-chain or branched alkyl or alkoxy radicals, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl or hexyl or methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy, tert-amyloxy or hexyloxy.
C2-C22alkenyl is, for example, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-dodec-2-enyl or n-octadec-4-enyl.
The C8-C20 fatty acid radicals defined for the quaternary ammonium compounds of the formula (1) are derived from saturated or unsaturated fatty acids, such as, for example, from capric, lauric, myristic, palmitic, stearic, dodecyl; pentadecyl; hexadecyl or oleyl acid; or decanoic, dodecanoic, tetradecanoic, hexadecanoic, oleic, linoleic, linolenic, ricinoleic acid, coconut fatty acid, or preferably tallow fatty acid.
Preferred photobleaching agents of the formula (2a) of the novel composition have the formula 
in which
PC, X2, X3, and R6 are as defined above;
M is hydrogen, an alkali metal ion, ammonium ion or amine salt ion; and the sum of the numbers r1 and r2 is from 1 to 4 and
As balances exactly the positive charge on the remainder of the molecule, and in particular the formula 
in which
PC is as defined in formula (2a),
R6xe2x80x2 is C2-C6alkylene;
r1 is a number from 1 to 4;
X3xe2x80x2 is a group of the formula 
xe2x80x83in which
R7 and R8 independently of one another are unsubstituted C1-C4alkyl or C1-C4alkyl substituted by hydroxyl, cyano, halogen or phenyl;
R9 is R7; cyclohexyl or amino;
R11 is C1-C4alkyl;
R21 is C1-C4alkyl; C1-C4alkoxy; halogen, carboxyl, carb-C1-C4alkoxy or hydroxyl; and
Axe2x80x3 is a halide, alkylsulfate or arylsulfate ion;
it being possible for the radicals xe2x80x94SO2NHRxe2x80x26xe2x80x94X3xe2x80x2+Axe2x88x92 to be identical or different.
Other photobleaching agents which can be used according to the invention have the formula 
in which
PC is the phthalocyanine ring system;
Me is Zn, Fe(II), Ca, Mg, Na, K, Alxe2x80x94Z1, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV), In(III), Sn(IV) or Hf(VI);
Z1 is a halide, sulfate, nitrate, carboxylate, alkanolate, or hydroxyl ion;
q is 0; 1; or 2;
Y3xe2x80x2 is hydrogen, an alkali metal ion or ammonium ion; and
r is any number from 1 to 4.
Very particularly preferred phthalocyanine compounds have the formula (5), in which
Me is Zn or Alxe2x80x94Z1; and
Z1 is a halide, sulfate, nitrate, carboxylate, alkanolate, or hydroxyl ion.
Other interesting phthalocyanine compounds which can be used according to the invention have the formula 
in which
PC, Me and q are as defined in formula (5);
R17xe2x80x2 and R18xe2x80x2 independently of one another are hydrogen, phenyl, sulfophenyl, carboxyphenyl, C1-C6alkyl, hydroxy-C1-C6alkyl, cyano-C1-C6alkyl, sulfo-C1-C6alkyl, carboxy-C1-C6alkyl or halogen-C1-C6alkyl or together with the nitrogen atom form the morpholine ring;
qxe2x80x2 is an integer from 2 to 6; and
r is a number from 1 to 4;
where, if r is  greater than 1, the radicals 
xe2x80x83present in the molecule may be identical or different.
Further interesting phthalocyanine compounds which can be used according to the invention have the formula 
in which
PC, Me and q are as defined in formula (5),
Yxe2x80x23 is hydrogen, an alkali metal ion or ammonium ion,
qxe2x80x2 is an integer from 2 to 6;
R17xe2x80x2 and R18xe2x80x2 independently of one another are hydrogen, phenyl, sulfophenyl, carboxyphenyl, C1-C6alkyl, hydroxy-C1-C6alkyl, cyano-C1-C6alkyl, sulfo-C1-C6alkyl, carboxy-C1-C6alkyl or halogen-C1-C6alkyl or together with the nitrogen atom form the morpholine ring;
mxe2x80x2 is 0 or 1; and
r and r1 independently of one another are any number from 0.5 to 3, the sum r+r1 being
at least 1, but no more than 4.
If the central atom Me in the phthalocyanine ring is Si(IV), the phthalocyanines used according to the invention may also have axial substituents (=R24) in addition to the substituents on the phenyl ring of the phthalocyanine ring. Such phthalocyanines have, for example, the formula 
in which
R24 is hydroxyl; C1-C22alkyl; branched C4-C22alkyl; C1-C22alkenyl; branched C4-C22alkenyl and mixtures thereof; C1-C22alkoxy; a sulfo or carboxyl radical; a radical of the formula 
xe2x80x83a branched alkoxy radical of the formula 
xe2x80x83an alkylethyleneoxy unit of the formula xe2x80x94(T1)dxe2x80x94(CH2)b(OCH2CH2)axe2x80x94B3 or an ester of the formula COOR23; and
U is [Q1]r+Asxe2x88x92; or Q2.
R16, R17, R18, R19, R20, R21, R22, R23, B2, B3, M, M1, Q1, Q2, As, T1, X1, Y2, Z2, a, b, c, d, e, r, v, w are as defined in the formulae (2a) and (2b).
Quaternary ammonium compounds of the component (b) preferably used according to the invention are compounds of the formula (1) in which
X1 is a halogen atom; xe2x80x94CH3SO4xe2x88x92; xe2x80x94C2H5SO4xe2x88x92; or xe2x80x94NO3xe2x88x92.
Quaternary ammonium compounds which are particularly preferably used according to the invention are those of the formula (1) in which
A and B independently of one another are the radical of the formula (1a) or (1b), or those compounds of the formula (1) in which A and B are the radical of the formula (1b).
Very particularly preferred quaternary ammonium compounds have the formula 
in which
R1, R2 and B are C1-C5alkyl;
R3 is the aliphatic radical of tallow fatty acid; and
X3xe2x88x92 is a halogen atom.
Further interesting quaternary ammonium compounds have the formula 
in which
R1 and R2 are C1-C5alkyl;
R3 is the aliphatic radical of tallow fatty acid and
X3xe2x88x92 is a halogen atom.
Preference is given to using fabric softener compositions comprising
(a) a water-soluble phthalocyanine of the formula (5); and
(b) a quaternary ammonium compound of the formula (8).
Preference is also given to using fabric softener compositions comprising
(a) a water-soluble phthalocyanine of the formula (10) and
(b) a quaternary ammonium compound of the formula (8).
The photobleaching agents used according to the invention are used in the fabric softener composition only in small amounts and thus have a catalytic effect.
The novel fabric softener compositions preferably comprise from 0.0001 to 0.05% by weight, preferably from 0.001 to 0.005% by weight, of component (a) and from 1 to 20% by weight, preferably from 5 to 20% by weight, of component (b).
The novel fabric softener composition may also comprise additives customary for standard commercial fabric softeners, such as alcohols, such as, for example, ethanol, n-propanol, i-propanol, polyhydric alcohols, such as, for example, glycerol and propylene glycol; amphoteric and nonionic surfactants, such as, for example, carboxyl derivatives of imidazole, oxethylated fatty alcohols, hydrogenated and ethoxylated castor oil, alkyl polyglycosides, for example decylpolyglucose and dodecylpolyglucose, fatty alcohols, fatty acid esters, fatty acids, ethoxylated fatty acid glycerides or fatty acid partial glycerides; also relatively small amounts of dyes, perfumes, buffer substances, inorganic or organic salts, such as, for example, water-soluble potassium, sodium or magnesium salts, non-aqueous solvents, pH buffers, hydrotropic agents, antifoams, corrosion inhibitors, antiredeposition agents, viscosity regulators, in particular polymeric or other thickeners, stabilisers, enzymes, optical brighteners, antishrink agents, stain removers, antimicrobial agents, germicides, fungicides, antioxidants, and anticrease agents.
The novel fabric softener composition is usually liquid. The active ingredients present therein are preferably emulsified in water. Preparation usually involves firstly stirring the active substance, i.e. the quaternary ammonium compound of the formula (1) in the molten state into water, then, where required, adding further desired additives and, finally, after cooling, adding the phthalocyanine compound as a diluted stock solution.
Another subject-matter of the invention is a process for the bleaching of textiles using a photobleaching agent, which comprises treating soiled textiles in a bath of a fabric softener composition comprising
(a) a water-soluble phthalocyanine of Zn, Fe(II), Ca, Mg, Na, K, Al, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV), Sn(III), Sn(IV) or Hf(VI) phthalocyanine; and
(b) a quaternary ammonium compound of the formula (1),
with irradiation with visible and/or infrared light or daylight, either on the fabric softener bath directly or on the damp textiles outside the fabric softener bath, and in the presence of oxygen.
The novel composition is used in the manner customary for known fabric softeners, the photobleaching agent only becoming effective upon irradiation with light, as described, for example, in U.S. Pat. No. 4,166,718. For example, textiles washed in a customary washing cycle are post-treated in a liquor comprising a novel fabric softener composition in a rinsing operation. Irradiation with visible and/or infrared light can be carried out directly in the fabric softener liquor, for example using a suitable artificial light source in the washing machine. Irradiation can, however, also be preferably carried out after the textiles have been removed from the rinsing bath in the damp state, the light source used preferably being sunlight. In this case, exposure can suitably be carried out while the textiles are drying. If the textiles are not dried on a line, but, for example, in a tumbledryer, exposure may also take place during this drying process, for example using a suitable artificial light source, fixed to or in the tumbledryer. For the photobleaching agent to be effective, the presence of oxygen is also required. The oxygen present (dissolved) in the wash liquor (the liquor should as far as possible contain no reducing agent) or the (dissolved) oxygen which is present in the liquor or atmospheric oxygen when exposure takes place outside the bath is sufficient.
Examples of suitable textile fibre materials which may be treated with the novel fabric softener composition are materials made of silk, wool, polyamide or polyurethanes, and in particular cellulosic fibre materials of all types. Examples of such fibre materials are the natural cellulose fibres, such as cotton, linen, jute and hemp, and also pulp and regenerated cellulose. Preference is given to textile fibre materials made of cotton. The novel fabric softener compositions are also suitable for hydroxyl group-containing fibres which are present in mixed fibres, for example mixtures of cotton with polyester fibres or polyamide fibres.
The effect of the photobleaching agent considerably improves removal of stains from the treated fabric. In addition, colour transfer between individual fabric articles can be prevented or reduced.
Furthermore, the novel composition has the advantage that the effect of the essential components is not mutually influenced, so that the bleaching effect of the photobleaching agent is not impaired by the quaternary ammonium compound and vice versa.